Processing method for silver halide color photographic light-sensitive material

ABSTRACT

Disclosed is a processing method for silver halide color photographic light-sensitive material in which a silver halide color photographic light-sensitive material is processed with a processing solution capable of fixation and then a part or all of the overflow from stabilizer is allowed to enter in the processing solution capable of fixing wherein said silver halide color photographic light-sensitive material contains a coupler represented by Formula 2eq-1 and said stabilizer contains substantially no formaldehyde but contains a compound represented by Formula I or Formula II: ##STR1## 
     
         R.sub.1 --O--(R.sub.2 --O).sub.m --X.sub.1                 (Formula I) 
    
      ##STR2## The total amount of silver coated in said silver halide color photographic light-sensitive material is not less than 3 g and not more than 10 g per m 2  of light-sensitive material; 
     said silver halide color photographic light-sensitive material contains a compound represented by the following formulae B-1 through B-3, ##STR3## the above constituents are defined in the specification. The processing method for silver halide color photographic light-sensitive material according to this invention offers good dye image preservability and improved staining in the unexposed portion and which permits waste liquid reduction and is hence excellent from the socio-environment viewpoint.

FIELD OF THE INVENTION

The present invention relates to a processing method for silver halidecolor photographic light sensitive material, more specifically to aprocessing method for silver halide color photographic light-sensitivematerial which offers good dye image preservability and improvedstaining in the unexposed portion and which permits waste liquidreduction and is hence excellent from the socio-environmental viewpoint.

BACKGROUND OF THE INVENTION

Silver halide photographic light-sensitive materials are typicallysubjected to imagewise exposure, after which they are processed in colordevelopment, bleaching, fixation or bleach-fixation, washing,stabilizing and other processes. It is a known fact that thiosulfate, acompound which forms a water-soluble complex salt upon reaction withsilver halide, other compounds which form water-soluble complex salts ofsilver, and sulfite, metabisulfite and other preservatives, all incontact with the light-sensitive material, enter in the washing processwhich follows the process using a processing solution capable offixation such as a fixer or bleach-fixer and adversely affect the imagepreservability in the case of small amounts of washing water. It istherefore a common practice to wash down the salts from the photographicmaterial with a large amount of water after processing with theprocessing bath capable of fixation to overcome this drawback.

In recent years, however, there have been increasing demands for aprocess which uses a reduced amount of washing water and which takes ameasure against environmental pollution for economic reasons such as ashortage of water resources and rises in sewage service fee and fuel,light expenses and for a reason of environmental concern.

Means of meeting these requirements include the method in which water isflown in countercurrent in a plurality of chambers of washing tank,described in West German Patent No. 2,920,222, S. R. Goldwasser, "WaterFlow Rate in Immersion-washing of Motion-picture Film", SMPTE. vol. 64,248 253, May (1955) and other publications.

Also known is the processing method in which a preliminary washing tankis provided immediately after the fixing bath to reduce the entrance ofpollutants in contact with the light-sensitive material into the washingprocess and reduce the amount of washing water.

However, none of these methods fully avoids the use of washing water.With the recent trends toward shortage of water resources and rise inwashing cost due to increased price of crude oil etc., these processingmethods are of great concern.

The present applicants proposed a processing method wherein developmentis followed immediately by stabilization without washing in JapanesePatent Publication Open to Public Inspection (hereinafter referred to asJapanese Patent O.P.I. Publication) Nos. 14834/1983, 34448/1983,132146/1982 and 18631/1983 and other publications to offer a solution tothe problems described above. However, even this method involves variousdrawbacks. For example, in conventional processing methods, the previousbath component transferred in adherence to light-sensitive material hasbeen diluted to high extent, since a large amount of water is used forwashing, which waste liquid can be discharged as such to rivers, sewers,etc. On the other hand, the stabilizing process described above resultsin much accumulation of the previous bath component in the stabilizer,which waste liquid cannot be discharged as such to rivers or sewersbecause it is banned by legal regulations on environmental pollution.This necessitates expensive commission of waste liquid recovery todedicated companies. Thus, huge expense is required to dispose the wasteliquid, though the washing water cost become zero.

A method of solving this problem is described by the present applicantsin Japanese Patent O.P.I. Publication Nos. 235133/1985, 212935/1988 andother publications. This method is characterized in that the overflowfrom stabilizing bath is allowed to enter in the processing bath capableof fixation, i.e., the previous bath.

However, even this method has some drawbacks; when the overflow fromstabilizer is allowed to enter in the previous bath capable of fixation,the preservative sulfite is consumed and sulfide precipitation occurstherein because formaldehyde is usually contained in the stabilizer forcolor negative films for the purpose of improving the image stability byclosing the active point of 4-equivalent coupler. As a means of solvingthis problem, there is a method using a stabilizer containingsubstantially no formaldehyde. Although this method avoids sulfideprecipitation, a problem of stain in the unexposed portion arises inrelation to the dye image stability in color negative films containing a4-equivalent magenta coupler.

To solve this problem, methods using a 2-equivalent coupler, describedin Japanese Patent O.P.I. Publication Nos. 54261/1987, 19660/1987 and298344/1988 have been proposed. However, these processing methods for2-equivalent coupler, wherein the overflow from the stabilizing bathwhich follows the processing bath capable of fixation is allowed toenter in the processing bath capable of fixation as the previous bath,were found to pose a problem of easy occurrence of staining in theunexposed portion and has a drawback of easy occurrence of reticulation.This tendency poses a major problem when the processing solution capableof fixation is replenished with a small amount of replenisher.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a processing methodfor silver halide color photographic light sensitive material whichcontains substantially no formaldehyde and which permits significantreduction in the amount of waste liquid and is hence excellent from thesocioenvironmental viewpoint.

It is another object of the invention to provide a processing method forsilver halide color photographic light-sensitive material which offersimprovements in the prevention of staining in the unexposed portion andreticulation.

It is still another object of the invention to provide a processingmethod for silver halide color photographic light-sensitive materialwhich is excellent in the storage stability of processing solutioncapable of fixation and which permits long-term stable processing.

The other objects will become obvious through the description whichfollows.

The processing method for silver halide color photographiclight-sensitive material of the present invention, in which a silverhalide color photographic light-sensitive material is processed with aprocessing solution capable of fixation whereafter a part or all of theoverflow from stabilizer is allowed to enter in the processing solutioncapable of fixation, is characterized in that said silver halide colorphotographic light-sensitive material contains a coupler represented byFormula 2eq-1 and said stabilizer contains substantially no formaldehydebut contains a compound represented by Formula I or II. ##STR4## whereinCp represents a coupler residue; * represents a coupler coupling site; Xrepresents a group which splits off upon dye formation by coupling withthe oxidation product of an aromatic primary amine based colordeveloping agent.

    R.sub.1 --O--R.sub.2 --O).sub.m X.sub.1                    Formula (I)

wherein R₁ represents a monovalent organic group; R₂ represents anethylene group, trimethylene group or propylene group; m represents aninteger of 4 to 50. X₁ represents a hydrogen atom, --SO₃ M or --PO₃ M₂,wherein M represents a hydrogen atom, alkali metal or ammonium. ##STR5##wherein R₉ represents a hydrogen atom, hydroxyl group, lower alkylgroup, alkoxy group, ##STR6##

R₁₀, R₁₁ and R₁₂, whether identical or not, independently represent ahydrogen atom or lower alkyl group, which lower alkyl group preferablyhas 1 to 4 carbon atoms, such as a methyl group, ethyl group or propylgroup; 1₁ through 1₃ independently represent an integer of 0 to 30; p,q₁ and q₂ independently represent an integer of 0 to 30.; X₁ and X2independently represent --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, ##STR7##

A preferred mode of embodiment of the present invention is that thetotal amount of silver coated in the silver halide color photographiclight-sensitive material is not less than 2 g per m² of light-sensitivematerial and the silver halide color photographic light-sensitivematerial contains a compound represented by the following formulae B-1through B-3. ##STR8## wherein R₁ represents an alkyl group, cycloalkylgroup, aryl group, hydroxyl group, alkoxycarbonyl group, amino group,carboxylic acid group (including its salt) or sulfonic acid group(including its salt). R² and R³ independently represent a hydrogen atom,halogen atom, amino group, nitro group, hydroxyl group, alkoxycarbonylgroup, carboxylic acid group (including its salt) or sulfonic acid group(including its salt). M represents a hydrogen atom, alkali metal orammonium group. ##STR9## wherein R⁴ represents a halogen atom, alkylgroup, aryl group, halogenated alkyl group, --R¹² --OR¹³, --CONHR¹⁴ (R¹²represents an alkylene group; R¹³ and R¹⁴ independently represent ahydrogen atom, alkyl group or arylalkyl group) or arylalkyl group; R⁵and R⁶ independently represent a hydrogen atom, halogen atom,halogenated alkyl group or alkyl group; R⁷ represents a hydrogen atom,halogen atom, alkyl group, aryl group, halogenated alkyl group,arylalkyl group, --R¹⁵ --R¹⁶ or --CONHR¹⁷ (R¹⁵ represents an alkylenegroup; R¹⁶ and R¹⁷ independently represent a hydrogen atom or alkylgroup); R⁸, R⁹, R¹⁰ and R¹¹ independently represent a hydrogen atom,halogen atom, hydroxyl group, alkyl group, amino group or nitro group.

Preferable processing procedures for the processing method using theprocessing solution according to the present invention are as follows.

(1) Color development→bleach-fixation→stabilization

(2) Color development→bleaching→bleach-fixation→stabilization

(3) Color development→bleaching→bleach-fixation→stabilization

(4) Color development→bleach-fixation→fixation→stabilization

(5) Color development→bleach-fixation→bleach-fixation→stabilization

(6) Colordevelopment→bleaching→bleach-fixation→fixation.fwdarw.stabilization

Preference is given to the procedures (1), (2) and (3). The processingsolution capable of fixation according to the present invention meansboth a bleach-fixer and fixer.

The compound represented by Formula I is exemplified by the followingcompounds. ##STR10##

These compounds represented by Formula I may be used in combination. Thetotal amount of their addition is 0.1 to 40 g, preferably 0.3 to 20 gper liter of stabilizer for the invention.

The compound represented by Formula II is exemplified by the followingcompounds. ##STR11##

These water-soluble organic siloxane compounds having a polyoxyalkylanegroup, represented by Formula II, may be used in combination. When usedin a total amount of 0.01 to 20 g per liter of stabilizer, they have agood effect particularly on the prevention of precipitation and flawswithout involving much deposition on the light-sensitive materialsurface.

The water-soluble organic siloxane compound for the present invention isan ordinary water-soluble organic siloxane compound as described inJapanese Patent O.P.I Publication Nos. 18333/1972 and 62128/1974,Japanese Patent Examined Publication Nos. 51172/1980 and 37538/1976,U.S. Pat. No. 3,545,970 and other publications.

These water-soluble organic siloxane compounds are commerciallyavailable from UCC (Union Carbide Company), Shin-Etsu Chemical Co., Ltd.and other suppliers.

Although the stabilizer for the present invention may be supplied from asingle bath, the number of baths may be increased within the range offrom about 2 to 10 baths, whereby the desired effect of the invention isenhanced. Although the replenisher for the stabilizer may be supplied inseveral steps, it is preferable to supply the replenisher to a bath andallow the overflow therefrom (including the case where the bath solutionpasses through a tube below the liquid surface level which communicatesthe two baths) to enter in the previous bath. It is more preferable touse two or more stabilizing baths, supply the stabilizer replenisher tothe final stabilizing bath, allow the overflow to sequentially enter inthe previous bath and allow a part or all of the overflow from thestabilizing bath which follows the processing solution capable offixation to enter in the processing solution capable of fixation,whereby the effect of the invention is enhanced. As the case may be, itis also acceptable to use two or more stabilizing baths and allow a partor all of the overflow from an intermediate stabilizing bath between thefirst and last stabilizing baths.

In the present invention, "to allow a part or all of the overflow fromthe stabilizer to enter in the processing solution capable of fixation"specifically includes the method in which the overflow is allowed todirectly enter through piping, the method in which the overflow is onceretained in a reservoir and then pumped or otherwise flown and themethod in which the overflow is flown after being prepared as areplenisher for the processing solution capable of fixation in a mixingtank.

In the present invention, "to contain substantially no formaldehyde"means that the formaldehyde content is 0 to 0.2 g per liter ofstabilizer. In the present invention, the amount of replenisher added tostabilizing bath is preferably not more than 800 ml per m² oflight-sensitive material, with more preference given to the range from100 to 620 ml, since excess reduction in the amount of replenisherresults in dye fading, post-drying salt separation on thelight-sensitive material surface and other problems.

More specific setting of the amount of replenisher varies depending onthe tank configuration of stabilizing bath; the amount of replenishercan be set at lower levels as the number of tanks increase.

The pH of the stabilizing bath for the present invention is preferably5.5 to 11.0, with more preference given to the range of from 7 to 10.5,more preferably 7.5 to 10 for enhancing the effect of the invention.Also, temperature is preferably 15° to 70° C., more preferably 20° to55° C. The stabilizing time for the invention is preferably not longerthan 120 seconds, more preferably 3 to 90 seconds, and still morepreferably 6 to 60 seconds.

In the present invention, it is preferable to add a chelating agenthaving an iron ion chelate stability constant of over 8 to thestabilizer. Here, the chelate stability constant is the constant whichis well known in L. G. Sillen and A. E. Martell, "Stability Constants ofMetal Ion Complexes", The Chemical Society, London (1964), S. Chaberekand A. E. Martell in "Organic Sequestering Agents", Wiley (1959) andother publications.

Examples of chelating agents having an iron ion chelate stabilityconstant of over 8 include organic carboxylic acid chelating agents,organic phosphoric acid chelating agents, inorganic phosphoric acidchelating agents and polyhydroxy compounds. The iron ion means theferric ion (Fe³⁺).

Examples of chelating agents having a ferric ion chelate stabilityconstant of over 8 include ethylenediaminediorthohydroxyphenylaceticacid, diaminopropanetetraacetic acid, nitrilotriacetic acid,hydroxyethylenediaminetriacetic acid, dihydroxyethyl glycine,ethylenediaminediacetic acid, ethylenediaminedipropionic acid,iminodiacetic acid, diethylenetriaminepentaacetic acid,hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid,trans-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylene-phosphonicacid, nitrilotrimethylenephosphonic acid,1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid,2-phosphonobutane-1,2,4-tricarboxylic acid,1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid,catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodiumtetrapolyphosphate and sodium hexametaphosphate, but these are not to beconstrued as limitative. Of these compounds,diethylenetriaminepentaacetic acid, nitrilotriacetic acid,nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonicacid and others are more preferable, with most preference given to1-hydroxyethylidene-1,1-diphosphonic acid.

The amount of the chelating agent is preferably 0.01 to 50 g, morepreferably 0.05 to 20 g per liter of stabilizer, in which content rangegood results are obtained.

Ammonium compounds are preferably added to the stabilizer, which aresupplied by ammonium salts of various inorganic compounds, includingammonium hydroxide, ammonium bromide, ammonium carbonate, ammoniumchloride, ammonium hypophosphite, ammonium phosphate, ammoniumphosphite, ammonium fluoride, acidic ammonium fluoride, ammoniumfluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammoniumhydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammoniumiodide, ammonium nitrate, ammonium pentaborate, ammonium acetate,ammonium adipate, ammonium laurin tricarboxylate, ammonium benzoate,ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate,ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate,ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate,ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammoniumethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammoniummaleate, ammonium oxalate, ammonium phthalate, ammonium picrate,ammonium pyrrolidinedithiocarbamate, ammonium salicylate, ammoniumsuccinate, ammonium sulfanylate, ammonium tartrate, ammoniumthioglycolate and 2,4,6-trinitrophenol ammonium.

These ammonium compounds may be used singly or in combination. Theamount of ammonium compound added is preferably 0.001 to 1.0 mol, morepreferably 0 002 to 2.0 mol per liter of stabilizer.

The stabilizer preferably contains a metal salt in combination with thechelating agent described above. Examples of such metal salts includesalts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Aland Sr, and it can be supplied as an inorganic salt such as halide,hydroxide, sulfate, carbonate, phosphate or acetate, or a water-solublechelating agent.

The amount of its addition is preferably 1×10⁻⁴ to 1×10⁻¹ mol, morepreferably 4×10⁻⁴ to 2×10⁻² mol per liter of stabilizer.

The stabilizer may contain an organic salt such as citrate, acetate,succinate, oxalate or benzoate, and a pH regulator such as malate,borate, hydrochloric acid or sulfate. These compounds may be used in anycombination, as long as the amount of their addition is necessary tomaintain the desired pH in the stabilizing bath and as long as it doesnot adversely affect the stability of color photographic images or theoccurrence of precipitation during storage.

In the present invention, one or more fungicides can be added, whethersingly or in combination, as long as the effect of the invention is notdegraded.

In the processing method of the present invention, silver may berecovered from the stabilizer. Examples of methods which serve well forthis purpose include the electrolytic method described in French PatentNo. 2,299,667, the precipitation method described in Japanese PatentO.P.I. Publication No. 73037/1977 and German Patent No. 2,331,220, theion exchange method described in Japanese Patent O.P.I. Publication No.17114/1976 and German Patent No. 2,548,237 and the metal replacementmethod described in British Patent No. 1,353,805.

For silver recovery, it is particularly preferable to recover silverfrom the tank solution on an in-line basis using the electrolytic methodor anion exchange resin method, since the rapid processing suitabilityimproves, but silver may be recovered from the overflow waste liquid andrecycled.

The stabilizer may be subjected to ion exchange treatment,electrodialytic treatment (Japanese Patent O.P.I. Publication No.28949/1986), reverse osmotic treatment (Japanese Patent O.P.I.Publication Nos. 240153/1985 and 254151/1987) and other treatments. Itis also preferable to use deionized water for the stabilizer. This isbecause the antifungal property, stability and image stability of thestabilizer improve.

Any means of deionization can be used, as long as the Ca and Mg ionconcentration of the treated washing water is not more than 5 ppm, andit is preferable to use an ion exchange resin or reverse osmoticmembrane treatment singly or in combination.

Ion exchange resins and reverse osmotic membranes are described inJournal of Technical Disclosure Nos. 87-1984 and 89-20511.

The salt concentration in the stabilizer is preferably not more than1000 ppm, more preferably not more than 800 ppm.

Although stabilizing need not be followed by washing, rinsing with asmall amount of water, surface washing, etc may be carried out asnecessary within a very short time.

The color developing agent used for the color developing processincludes amino phenol compounds and p-phenylenediamine compounds. In thepresent invention, p-phenylenediamine compounds having a water-solublegroup are preferred.

At least one water-soluble group is present on the amino group orbenzene nucleus of the p-phenylenediamine compound. Examples ofpreferred water-soluble groups include:

    --(CH.sub.2).sub.n --CH.sub.2 OH,

    --(CH.sub.2).sub.m --NHSO.sub.2 --(CH.sub.2).sub.n --CH.sub.3,

    --(CH.sub.2).sub.m --O--(CH.sub.2).sub.n --CH.sub.3,

    --(CH.sub.2 CH.sub.2 O).sub.n C.sub.m H.sub.2m+1

(m and n independently represent an integer), --COOH group and --SO₃ Hgroup.

Examples of color developing agents preferably used for the presentinvention are given below. ##STR12##

Of the color developing agents shown above, Exemplified Compound Nos.A-1, A-2, A-3, A-4, A-6, A-7 and A 15 are preferred.

The amount of color developing agent added is preferably not less than0.5×10⁻² mol, more preferably 1.0×10⁻² to 1.0×10⁻¹ mol, and ideally1.5×10⁻² to 7.0×10⁻² mol per liter of color developer.

The color developing agent is used normally in the form of a salt suchas hydrochloride, sulfate or p-toluenesulfonate.

The color developer used for the color developing process may contain analkali which is commonly used in developer, such as sodium hydroxide,potassium hydroxide, ammonium hydroxide, sodium carbonate, potassiumcarbonate, sodium sulfate, sodium metaborate or borax, and may alsocontain various additives such as benzyl alcohol, a halogenated alkalisuch as potassium bromide or potassium chloride, and citrazinic acid asa development regulator, hydroxylamine, a hydroxylamine derivative suchas diethylhydroxylamine, a hydrazine derivative such ashydrazinodiacetic acid or sulfite as a preservative.

Various defoaming agents and surfactants and organic solvents such asmethanol, dimethylformamide and dimethylsulfoxide may also be added. ThepH of the color developer is normally not less than 7, preferably 9 to13.

The color developer may contain as necessary an antioxidant such astetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone,hydroxamic acid, pentose, hexose or pyrogallol-1,3-dimethyl ether.

The color developer may contain various chelating agents as sequesteringagents. Examples thereof include aminopolycarboxylic acids such asethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,organic phosphonic acids such as 1 hydroxyethylidene-1,1-diphosphonicacid, aminopolyphosphonic acids such as aminotri(methylenephosphonicacid) and ethylenediaminetetraphosphonic acid, oxycarboxylic acids suchas citric acid and gluconic acid, phosphonocarboxylic acids such as2-phosphonobutane-1,2,4-tricarboxylic acid and polyphosphoric acids suchas tripolyphosphoric acid and hexametaphosphoric acid.

In continuous processing, the amount of color developer replenisher ispreferably not more than 1.5 1, more preferably 250 to 900 ml, and stillmore preferably 300 to 700 ml per 1.0 m² of light-sensitive material fora color negative film.

The bleaching agent used in the bleacher or bleach-fixer for the presentinvention includes the ferric complex salts of organic acid representedby the following formula A or B and ferric complex salts of ExemplifiedCompound Nos. A'-1 through 16. ##STR13## wherein A₁ through A₄, whetheridentical or not, independently represent --CH₂ OH, --COOM or --PO₃ M₁M₂ (M, M₁ and M₂ independently represent a hydrogen atom, alkali metalor ammonium); X represents a substituted or unsubstituted alkylene grouphaving 3 to 6 carbon atoms. ##STR14## wherein A₁ through A₄ have thesame definitions as with Formula A; n represents an integer of 1 to 8.B₁ and B₂, whether identical or not, independently represent asubstituted or unsubstituted alkylene group having 2 to 5 carbon atoms.

The compound represented by Formula A is described in detail.

A₁ through A₄, whether identical or not, independently represent --CH₂OH, --COM or --PO₃ M₁ M₂ (M, M₁ and M₂ independently represent ahydrogen atom, alkali metal such as sodium or potassium, or ammonium); Xrepresents a substituted or unsubstituted alkylene group having 3 to 6carbon atoms such as trimethylene, tetramethylene or pentamethylene.Examples of the substituent include hydroxyl groups and alkyl groupshaving 1 to 3 carbon atoms.

Preferred compounds represented by Formula A are exemplified as follows.##STR15##

Ferric complex salts of these compounds A-1 through A-12 may be used inthe form of sodium salt, potassium salt or ammonium salt. From theviewpoint of the desired effect of the invention and solubility,ammonium salts of these ferric complex salts are preferably used.

Of the compounds shown above, A-1, A-3, A-4, A-5 and A-9 are preferablyused, with more preference given to A-1.

The compound represented by Formula B is described in detail.

A₁ through A₄ have the same definitions as with Formula A; n representsan integer of 1 to 8. B₁ and B₂, whether identical or not, independentlyrepresent a substituted or unsubstituted alkylene group having 2 to 5carbon atoms, such as ethylene, trimethylene, tetramethylene orpentamethylene. Examples of the substituent include hydroxyl groups andlower alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl andpropyl groups.

Preferred compounds represented by Formula B are exemplified as follows.##STR16##

Ferric complex salts of these compounds B-1 through B-7 may be used inthe form of sodium salt, potassium salt or ammonium salt.

Of the compounds shown above, B-1, B-2 and B-7 are preferably used forthe present invention, with more preference given to B-1.

The amount of ferric complex salt of organic acid added is preferably0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol per liter of bleacher.

Examples of preferable bleaching agents based on an iron complex salt ofa compound represented by Formula A or B for the bleacher or bleachfixer include ferric complex salts of the following compounds such assalts of ammonium, sodium, potassium and triethanolamine, but these arenot to be construed as limitative.

A'-1: Ethylenediaminetetraacetic acid

A'-2: trans-1,2-cyclohexanediaminetetraacetic acid

A'-3: Dihydroxyethylglycine

A'-4: Ethylenediaminetetrakismethylenephosphonic acid

A'-5: Nitrilotrismethylenephosphonic acid

A'-6: Diethylenetriaminepentakismethylenephosphonic acid

A'-7: Diethylenetriaminepentaacetic acid

A'-8: Ethylenediaminediorthohydroxyphenylacetic acid

A'-9: Hydroxyethylethylenediaminetriacetic acid

A'-10: Ethylenediaminedipropionic acid

A'-11: Ethylenediaminediacetic acid

A'-12: Hydroxyethyliminodiacetic acid

A'-13: Nitrilotriacetic acid

A'-14: Nitrilotripropionic acid

A'-15: Triethylenetetraminehexaacetic acid

A'-16: Ethylenediaminetetrapropionic acid

The bleacher may incorporate one or more ferric complex salts of thecompounds A'-1 through A'-16 in combination with a ferric complex saltof the compound represented by Formula A or B.

When using two or more ferric complex salts of organic acid incombination, it is preferable for the enhancement of the effect of thepresent invention that the ferric complex salt of a compound representedby Formula A or B account for not less than 70 mol %, more preferablynot less than 80 mol %, still more preferably not less than 90 mol %,and ideally not less than 95 mol %.

The iron (III) complex salt of organic acid may be used in the form of acomplex salt as such or may be converted to an iron (III) ion complexsalt by reaction in a solution between an iron (III) salt such as ferricsulfate, ferric chloride, ferric acetate, ferric ammonium sulfate orferric phosphate and aminopolycarboxylic acid or its salt. When using inthe form of a complex salt as such, one or more complex salts may beused. When using a ferric salt and aminopolycarboxylic acid to form acomplex salt in a solution, one or more ferric salts may be used.Similarly, one or more aminopolycarboxylic acids may be used.

In either case, aminopolycarboxylic acid may be used in excess for theformation of iron (III) ion complex salt.

The bleach-fixer or bleacher containing the iron (III) ion complex mayincorporate an ion complex salt of a metal other than iron, such ascobalt, copper, nickel or zinc.

The rapid processing effect can be enhanced by incorporating in thebleacher, bleach-fixer or fixer at least one of the imidazole describedin Japanese Patent O.P.I. Publication No. 295258/1989 and itsderivatives and the compounds represented by the formulas I through IXdescribed in the same patent application.

In addition to the bleaching accelerators described above, it ispossible to use the compounds exemplified in Japanese Patent ApplicationNo. 123456/1987, pp. 51-115, the compounds exemplified in JapanesePatent O.P.I. Publication No. 17445/1988, pp. 22-25, and the compoundsdescribed in Japanese Patent O.P.I. Publication Nos. 95630/1978 and28426/1978.

These bleaching accelerators may be used singly or in combination. Theamount of their addition is preferably about 0.01 to 100 g, morepreferably 0.05 to 50 g, and ideally 0.05 to 15 g per liter of bleacher.

The bleaching accelerator may be added and dissolved as such, but it isthe common practice to add it in solution in water, alkali or organicacid, and an organic solvent such as methanol, ethanol or acetone may beappropriately used to dissolve it before its addition.

The temperature of the bleacher or bleach-fixer is normally 20° to 50°C., and desirably 25° to 45° C.

The pH of the bleacher is preferably not more than 6.0, more preferablynot less than 1.0 and not more than 5.5. The pH of the bleach-fixer ispreferably 5.0 to 9.0, more preferably 6.0 to 8.5.

It should be noted that the pH of the bleacher or bleach-fixer means thepH in the silver halide light-sensitive material processing bath and isclearly differentiated from the pH of the replenisher.

The bleacher or bleach-fixer normally incorporates a halide such asammonium bromide, potassium bromide or sodium bromide. Variousfluorescent brightening agents, defoaming agents and surfactants may beadded.

The amount of replenisher for bleacher or bleach-fixer is normally notmore than 500 ml, preferably 20 to 400 ml, and ideally 40 to 350 ml perm² of silver halide color photographic light-sensitive material. As theamount of replenisher decreases, the effect of the present inventionincreases.

In the present invention, to increase the activity of the bleacher orbleach-fixer, air or oxygen sparging may be carried out in theprocessing bath and in the replenisher storage tank if necessary, and anappropriate oxidant such as hydrogen peroxide, hydrobromate orpersulfate may be appropriately added.

The fixing agent used in the fixer or bleach-fixer for the presentinvention is preferably a thiocyanate or thiosulfate. The amount ofthiocyanate is preferably at least 0.1 mol/l, more preferably not lessthan 0.3 mol/l, and still more preferably not less than 0.5 mol/l forprocessing a color negative film. The amount of thiosulfate ispreferably at least 0.2 mol/l, more preferably not less than 0.5 mol/lfor processing a color negative film.

In addition to these fixing agents, the fixer or bleach-fixer for thepresent invention may contain one or more pH buffers selected from thegroup comprising various acids and salts such as boric acid, borax,sodium hydroxide, potassium hydroxide, sodium carbonate, potassiumcarbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,sodium acetate and ammonium hydroxide.

It is also desirable to add a large amount of a rehalogenating agentsuch as an alkali halide or ammonium halide, e.g., potassium bromide,sodium bromide, sodium chloride or ammonium bromide. Compounds which areknown as additives to fixer or bleach-fixer such as alkylamines andpolyethylene oxides may also be added.

Silver may be recovered from the fixer or bleach-fixer for the presentinvention by a known method.

The amount of replenisher for the fixer or bleach-fixer for theinvention is preferably not more than 900 ml, more preferably 20 to 750ml, and ideally 50 to 620 ml per m² of light-sensitive material. The pHof the fixer is preferably 4 to 8.

A compound represented by the formula FA described in Japanese PatentApplication No. 295258/1989, pp. 56 may be added to the processingsolution capable of fixation for the present invention, which not onlyenhances the effect of the invention but also offers an additionaleffect in that sludge formation in the processing solution capable offixation is significantly suppressed during prolonged processing of asmall amount of light-sensitive material.

The compound represented by Formula FA can be synthesized by the methodsdescribed in U.S. Pat. Nos. 3,335,161 and 3,260,718. These compoundsrepresented by Formula FA may be used singly or in combination.

Use of these compounds represented by Formula FA yields good resultswhen they are added in an amount of 0.1 to 200 g per liter of processingsolution.

Although the processing times respectively for the bleacher and fixerfor the present invention may be set at any level, each processing timeis preferably shorter than 3 minutes and 30 seconds, more preferably 10seconds to 2 minutes and 20 seconds, and ideally 20 seconds to 1 minuteand 20 seconds. The processing time with bleach fixer is preferablyshorter than 4 minutes, more preferably 10 seconds to 2 minutes and 20seconds.

In the processing method of the present invention, it is a preferredmode of embodiment to conduct forced stirring of the bleacher,bleach-fixer or fixer. This is because it not only enhances the desiredeffect of the invention but also improves the rapid processingsuitability. Here, forced stirring does not imply ordinary diffusivemigration of solution but implies stirring by means of a stirrer. Thisforced stirring can be achieved by the methods described in JapanesePatent O.P.I. Publication Nos. 222259/1989 and 206343/1989.

In the present invention, prevention of bleach fogging, an additionaleffect of the invention, is effected when the crossover time between thecolor developing bath and the bleaching or bleach-fixing bath is within10 seconds, preferably within 7 seconds.

The silver halide grains for the silver halide color photographiclight-sensitive material (hereinafter referred to as the light-sensitivematerial or sensitive-material, where necessary) may comprise silverchloride, silver chlorobromide, silver iodobromide or silverchloroiodobromide, with preference given to silver iodobromide from theviewpoint of enhancement of the effect of the invention.

The average silver iodide content of the entire silver halide emulsionin the light-sensitive material is preferably 0.1 to 15 mol %, morepreferably 0.5 to 12 mol %, and ideally 1 to 10 mol %.

The total amount of silver coated in the light-sensitive material ispreferably not less than 2 g, more preferably not less than 3 g and notmore than 10 g per m² of light-sensitive material.

The average grain size of the entire silver halide emulsion in thelight-sensitive material is preferably not more than 2.0 μm, morepreferably 0.1 to 1.2 μm.

When the silver halide emulsion contains grains having an average valueof less than 5 for grain size/grain thickness ratio, it is preferablefrom the viewpoint of desilvering property that the grain sizedistribution be monodispersed.

Here, grain diameter is defined as the diameter of the silver halidegrain when it is spherical or the diameter converted from a circle withthe same area from the projected image of the silver halide grain whenit is not spherical.

A highly monodispersed emulsion preferred for the present invention hasa distribution width of not more than 20%, more preferably not more than15%, defined by the following equation.

    (Grain size standard deviation/average grain diameter)×100=distribution width (%)

The crystal configuration of the silver halide grains may be normalcrystal, twin crystal or any other crystal, and any ratio of the [1.0.0]plane and the [1.1.1] plane is usable. With respect to the crystalstructure of these silver halide grains, it may be uniform from the coreto the outer portion and may be of the core shell type wherein the coreand the outer portion are of different layer structures. These silverhalides may be of the type wherein latent images are formed mainly onthe surface, or of the type wherein latent images are formed mainlyinside the grains. Moreover, tabular grains of silver halide such asthose described in Japanese Patent O.P.I. Publication No. 113934/1983and Japanese Patent Application No. 170070/1984 may be used.

The silver halide grains may be prepared by any of the acid method,neutral method, ammoniacal method and other methods.

It is also possible to use the method in which seed grains are formed bythe acid method and are grown to a given size by the ammoniacal method.In growing silver halide grains, it is preferable to control the pH, pAgand other factors in the reactor and to sequentially add and mix silverions and halide ions in an amount according to the rate of growth ofsilver halide grains described in Japanese Patent O.P.I. Publication No.48521/1979 at the same time.

The silver halide grains are preferably prepared as above. Thecomposition containing said silver halide grains is referred to assilver halide emulsion.

These silver halide emulsions may be chemically sensitized with activegelatin, sulfur sensitizers such as allylthiocarbamide, thiourea andcystine, selenium sensitizers, reduction sensitizers such as stannate,thiourea dioxide and polyamine, noble metal sensitizers such as goldsensitizers, specifically potassium aurothiocyanate, potassiumchloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, sensitizersbased on water-soluble salts such as ruthenium, palladium, platinum,rhodium and iridium, specifically ammonium chloropalladate, potassiumchloroplatinate and sodium chloropalladate (some of which act as asensitizer or antifogging agent, depending upon the amount), used singlyor in combination (e.g., a gold sensitizer and a sulfur sensitizer, anda gold sensitizer and a selenium sensitizer).

The silver halide emulsion is chemically ripened by the addition of asulfur-containing compound. Before, during or after this chemicalripening, at least one nitrogen-containing heterocyclic compoundcontaining at least one hydroxytetrazaindene and a mercapto group may beadded.

The silver halide may be optically sensitized by the addition of asensitizing dye at 5×10⁻⁸ to 3×10⁻³ mol per mol of silver halide, forinstance, in order to provide light sensitivity in the desiredwavelength range. Various sensitizing dyes can be used, whether singlyor in combination.

The coupler represented by Formula 2eq-1 for the present invention(hereinafter referred to as 2-equivalent coupler, where necessary) isdescribed below. ##STR17## wherein Cp represents a coupler residue; *represents a coupler coupling site; X represents a group which splitsoff upon dye formation by coupling with the oxidation product of anaromatic primary amine based color developing agent.

Typical examples of the yellow coupler residue represented by Cp aregiven in U.S. Pat. Nos 2,298,443, 2,407,210, 2,875,057, 3,048,194,3,265,506 and 3,447,928, "Farbkupplereine Literaturubersiecht AgfaMitteilung (Band II)", pp. 126-156 (1961) and other publications. Ofthese yellow coupler residues, acylacetoanilides such asbenzoylacetoanilide and pivaloylacetoanilide are preferred.

Typical examples of the magenta coupler residue are given in U.S. Pat.Nos. 2,369,489, 2,343,703, 2,311,082, 2,600,788, 2,908,573, 3,062,653,3,152,896, 3,519,429, 3,725,067 4,540,654 and Japanese Patent O.P.I.Publication No. 162548/1984, the above-mentioned Agfa Mitteilung (BandII), pp. 126-156 (1961) and other publications. Of these magenta couplerresidues, pyrazolones or pyrazoloazoles such as pyrazoloimidazole andpyrazolotriazole are preferred.

Typical examples of the cyan coupler residue are given in U.S. Pat. Nos.2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,895,826, 3,002,836,3,034,892 and 3,041,236, the above-mentioned Agfa Mitteilung (Band II),pp. 156-175 (1961) and other publications. Of these cyan couplerresidues, phenols or naphthols are preferred.

Examples of the leaving group represented by X include halogen atoms,monovalent groups such as an alkoxy group, aryloxy group, heterocyclicoxy group, acyloxy group, alkylthio group, arylthio group, heterocyclicthio group ##STR18## (wherein X₁ represents a group of atoms necessaryto form a 5- or 6-membered ring along with at least one atom selectedfrom the nitrogen atom, carbon atom, oxygen atom, nitrogen atom andsulfur atom in the formula), acylamino group and sulfonamide group, anddivalent groups such as an alkylene group; when the leaving group is adivalent group, X forms a dimer.

Examples of the leaving group are given below. Halogen atoms: Chlorine,bromine, fluorine ##STR19##

The 2-equivalent yellow coupler is preferably represented by Formula2-eq-2 or 2eq-3. ##STR20##

With respect to Formulas 2eq-2 and 2eq-3, R₁ and R₂ independentlyrepresent a hydrogen atom or substituent; k and 1 independentlyrepresent an integer of 1 to 5, when k and 1 are 2 or more, R₁ and R₂may be identical or not; X has the same definition as X in Formula2eq-1.

Examples of the substituent represented by R₁ or R₂ include halogenatoms, alkyl, cycloalkyl, aryl, heterocyclic and other groups which binddirectly or via a divalent atom or group.

Examples of the divalent atom or group include an oxygen atom, nitrogenatom, sulfur atom, carbonylamino, aminocarbonyl, sulfonylamino,aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonyl, ureylene,thioureylene, thiocarbonylamino, sulfonyl and sulfonyloxy.

The alkyl, cycloalkyl, aryl and heterocyclic groups exemplified for thesubstituent represented by R₁ or R₂ include those having a substituent.Examples of the substituent include halogen atoms, nitro, cyano, alkyl,alenyl, cycloalkyl, aryl, alkoxyl, aryloxy, alkoxycarbonyl,aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino,ureide, urethane, sulonamide, heterocyclic ring, arylsulfonyl,alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imidoand acyl groups.

With respect to the 2-equivalent yellow coupler, examples of X includethose exemplified for Formula 2eq-1, with preference given to an aryloxygroup and ##STR21## (wherein X₁ has the same definition as X₁ above).

Formula 2eq-2 includes the cases where R₁ or X forms a dimer or higherpolymer. Formula 2eq-3 includes the cases where R₁, R₂ or X forms adimer or higher polymer.

The 2-equivalent magenta coupler is preferably represented by formula2eq-4, 2eq-5, 2eq-6 or 2eq-7. ##STR22##

With respect to Formulas 2eq-4 through 2eq-7, R₃ represents asubstituent; R₁, R₂, X and l have the same definitions as R₁, R₂, X andl in formulae 2eq-2 and 2eq-3; when l is 2 or more, the R₂ groups may beidentical or not.

Examples of R₁ and R₂ include those exemplified for R₁ and R₂ in Formula2eq-3. Examples of R₃ include alkyl, cycloalkyl, aryl and heterocyclicgroups. These include those having a substituent. Examples of thesubstituent include those exemplified as the substituent possessed bythe groups exemplified for R₁ and R₂ in Formula 2eq-2.

With respect to the 2-equivalent magenta coupler, examples of X includethose exemplified for Formula 2eq-1, with preference given to a halogenatom, alkylthio group, arylthio group, aryloxy group, acyloxy group,##STR23## (wherein X₁ has the same definition as xl above) and alkylenegroup.

Formulae 2eq-4 and 2eq-5 include the cases where R₂, R₃ or X forms adimer or higher polymer. Formulas 2eq-6 and 2eq-7 include the caseswhere R₁, R₂ or X forms a dimer or higher polymer.

The 2-equivalent cyan coupler is preferably represented by Formula2eq-8, 2eq-9 or 2eq-10. ##STR24##

In these Formulae, R₂ and R₃ have the same definitions as R₂ and R₃ inFormula 2eq-4; R₄ represents a substituent; m represents an integer of 1to 3; n represents an integer of 1 or 2; p represents an integer of 1 to5; when m, n and p are 2 or more, the R₂ groups may be identical or not.

Examples of R₂ and R₃ include those exemplified for Formula 2eq-4.Examples of R₄ include those exemplified for R₃ in Formula 2eq-4.

With respect to the 2-equivalent cyan coupler, examples of X includethose exemplified for Formula 2eq-1, with preference given to a halogenatom, alkoxy group, aryloxy group and sulfonamide group.

Formulas 2eq-8 and 2eq-10 include the cases where R₂, R₃ or X forms adimer or higher polymer. Formula 2eq-9 includes the cases where R₂, R₃,R₄ or X forms a dimer or higher polymer.

Examples of the 2-equivalent couplers for the present invention aregiven below. ##STR25##

In the present invention, two or more yellow couplers may be used incombination. The total amount of their addition is preferably 5×10⁻⁵ to2×10⁻³ mol/m², more preferably 1×10⁻⁴ to 2×10⁻³ mol/m², and ideally2×10⁻⁴ to 2×10⁻³ mol/m². Two or more magenta couplers may be used incombination. The of their addition is preferably 2×10⁻⁵ to 1×10⁻³mol/m², more preferably 5×10⁻⁵ to 1×10⁻³ mol/m², and ideally 1×10⁻⁴ to1×10⁻³ mol/m². Two or more cyan couplers may be used in combination. Theof their addition is preferably 5×10⁻⁵ to 2×10⁻³ mol/m², more preferably1×10⁻⁴ to 2×10⁻³ mol/m², and ideally 2×10⁻⁴ to 2×10⁻³ mol/m².

In the present invention, the light-sensitive silver halide emulsionlayer incorporates a 2-equivalent coupler, which may be used incombination with a 4-equivalent coupler. When using a 4-equivalentcoupler, the 2-equivalent coupler content is preferably 50 to 100 mol %of the total coupler content, with the remaining part accounted for bythe 4-equivalent coupler. It is more preferable that the 2-equivalentcoupler account for 70 to 100 mol %, ideally 100 mol %, i.e., the totalcoupler content be accounted for by the 2-equivalent coupler.

Here, the 4-equivalent coupler is a coupler having no substituent at thecoupling site. The yellow coupler is preferably an acylacetoanilide suchas pivaloylacetoanilide or benzoylacetoanilide. The magenta couplerinclude indazolones, cyanoacetyls, 5-pyrazolones, and pyrazoloazolessuch as pyrazoloimidazole and pyrazolotriazole, with preference given to5-pyrazolones and pyrazoloazoles. The cyan coupler is preferably aphenol or naphthol.

Examples of 4-equivalent couplers which can be preferably used incombination include those represented by Formulae 2eq-2 through 2eq-10wherein X at the coupling site is a hydrogen atom. Examples of R₁through R₄ include those exemplified for Formulas 2eq-2 through 2eq-10,including the cases where R₁ through R₄ form a dimer or higher polymer.

In the present invention, various other couplers may be used incombination. Examples thereof are given in the following ResearchDisclosure Numbers.

The following table gives where relevant descriptions appear. The4-equivalent couplers described in the Research Disclosure Numbers maybe used in combination.

    ______________________________________    Item          Page in RD308119                               RD17643/RD18716    ______________________________________    Yellow coupler                  1001, VII-Term D                               VII-Terms C-G    Magenta coupler                  1001, VII-Term D                               VII-Terms C-G    Cyan coupler  1001, VII-Term D                               VII-Terms C-G    Colored coupler                  1002, VII-Term G                               VII-Term G    DIR coupler   1001, VII-Term F                               VII-Term F    BAR coupler   1002, VII-Term F    Other couplers which                  1001, VII-Term F    release a useful    residue    Alkali-soluble coupler                  1001, VII-Term E    ______________________________________

The additives used for the present invention can be added by dispersionas described in RD308119 XIV and by other methods.

In the present invention, the supports described in RD17643, p. 28,RD18716, pp. 647-648 and RD308119 XIX can be used.

The light-sensitive material for the present invention may be providedwith auxiliary layers such as a filter layer and interlayer as describedin RD308119, VII-Term K.

The light-sensitive material for the invention can take various layerconfigurations such as the ordinary, reverse and unit structuresdescribed in RD308119, VII-Term K.

When a vinyl sulfone hardener is used in the light-sensitive material,the effect of the present invention is enhanced.

The vinyl sulfone hardener is a compound having a vinyl group bound to asulfonyl group or a group capable of forming a vinyl group, preferablyhaving two or more vinyl groups bound to a sulfonyl group or two or moregroups capable of forming a vinyl group.

The compound represented by Formula VS-I is preferably used for thepresent invention.

    L--(SO.sub.2 --X).sub.m                                    Formula VS-I

wherein L represents an m-valent bonding group; X represents --CH═CH₂ or--CH₂ CH₂ Y wherein Y represents a group capable of splitting off in theform of HY upon reaction with base, such as a halogen atom, sulfonyloxygroup, sulfoxy group (including its salt) or tertiary amine residue; mrepresents an integer of 2 to 10; when m is 2 or more, the -SO₂ --Xgroups may be identical or not.

The m-valent bonding group L is an m-valent group formed with one ormore members selected from the group comprising aliphatic hydrocarbongroups such as alkylene, alkylidene, alkylidine and groups formedtherewith, aromatic hydrocarbon groups such as arylene and groups formedtherewith, --O--, --NR'-- (R' represents a hydrogen atom or an alkylgroup having preferably 1 to 15 carbon atoms), --S--, ##STR26## --CO,--SO--, --SO₂ -- or --SO₃ --; when two or more --NR'-- groups arepresent, the R' groups therein may bind together to form a ring.

The bonding group L includes those having a substituent such as ahydroxyl group, alkoxy group, carbamoyl group, sulfamoyl group, alkylgroup or aryl group.

X is preferably --CH₂ ═CH₂ or --CH₂ CH₂ Cl.

Examples of vinyl sulfone hardeners are given below. ##STR27##

Examples of the vinyl sulfone hardener for the present invention includethe aromatic compounds described in German Patent No. 1,100,942 and U.S.Pat. No. 3,490,911, the alkyl compounds bound via hetero atom describedin Japanese Patent Examined Publication Nos. 29622/1969, 25373/1972 and24259/1972, the sulfonamide ester compounds described in Japanese PatentExamined Publication No. 8736/1972, the1,3,5-tris[β-(vinylsulfonyl)propionyl]-hexahydro-s-triazine described inJapanese Patent O.P.I. Publication No. 24435/1974 and the alkylcompounds described in Japanese Patent Examined Publication No.35807/1975 and Japanese Patent O.P.I. Publication No. 44164/1976 and thecompounds described in Japanese Patent O.P.I. Publication No.18944/1984.

These vinyl sulfone hardeners are used in solution in water or organicsolvent in a ratio of 0.005 to 20% by weight, preferably 0.02 to 10% byweight of binder such as gelatin. Their addition to the photographiclayer is achieved by the batch method or in-line addition method, forinstance.

The layers to add these hardeners thereto are not subject to limitation;for example, the hardeners may be added to the uppermost layer alone,the lowermost layer alone or all layers.

In the present invention, the silver halide color photographiclight-sensitive material preferably contains a compound represented byone of Formulae B-1 through B-3. ##STR28## wherein R¹ represents analkyl group, cycloalkyl group, aryl group, hydroxyl group,alkoxycarbonyl group, amino group, carboxylic acid group (including itssalt) or sulfonic acid group (including its salt). R² and R³independently represent a hydrogen atom, halogen atom, amino group,nitro group, hydroxyl group, alkoxycarbonyl group, carboxylic acid group(including its salt) or sulfonic acid group (including its salt). Mrepresents a hydrogen atom, alkali metal or ammonium group. ##STR29##wherein R⁴ represents a hydrogen atom, halogen atom, alkyl group, arylgroup, halogenated alkyl group, --R¹² --OR¹³, --CONHR¹⁴ (R¹² representsan alkylene group; R¹³ and R¹⁴ independently represent a hydrogen atom,alkyl group or arylalkyl group) or arylalkyl group; R⁵ and R⁶independently represent a hydrogen atom, halogen atom, halogenated alkylgroup or alkyl group; R⁷ represents a hydrogen atom, halogen atom, alkylgroup, aryl group, halogenated alkyl group, arylalkyl group, --R¹⁵ --R¹⁶or --CONHR¹⁷ (R¹⁵ represents an alkylene group; R¹⁶ and R¹⁷independently represent a hydrogen atom or alkyl group); R⁸, R⁹, R¹⁰ andR¹¹ independently represent a hydrogen atom, halogen atom, hydroxylgroup, alkyl group, amino group or nitro group.

The compound represented by Formula B-1 is exemplified as follows.##STR30##

The compound represented by Formula B-1 is commercially available and iseasily available by those skilled in the art.

Of the compounds exemplified above, Compound Nos. B-1-1, B-1-2, B-1-3,B-1-4 and B-1-5 are preferable.

The compound of Formula B-1 for the present invention may be used incombination of two or more kinds. It is preferable to use it in a of0.03 to 50 g, more preferably 0.12 to 10 g, and still more preferably0.15 to 5 g per liter of the stabilizer for the invention.

Examples of the compounds represented by Formulae B-2 and B-3 are givenbelow.

B-2-1: 2-methyl-4-isothiazolin-3-one

B-2-2: 5-chloro-2-methyl-4-isothiazolin-3-one

B-2-3: 2-methyl-5-phenyl-4-isothiazolin-3-one

B-2-4: 4-bromo-5-chloro-2-methyl-4-isothiazolin 3 one

B-2-5: 2-hydroxymethyl-4-isothiazolin-3-one

B-2-6: 2-(ethoxyethyl)-4-isothiazolin-3-one

B-2-7: 2-(N-methyl-carbamoyl)-4-isothiazolin-3-one

B-2-8: 5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-isothiazolin-3-one

B-2-9: 5-chloro-2-(2-phenylethyl)-4-isothiazolin-3-one

B-2-10: 4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one

B-3-1: 1,2-benzisothiazolin-3-one

B-3-2: 2-(2-bromoethyl)-1,2-benzisothiazolin-3-one

B-3-3: 2-methyl-1,2-benzisothiazolin-3-one

B-3-4: 2-ethyl-5-nitro-1,2-benzisothiazolin-3-one

B-3-5: 2-benzyl-1,2-benzisothiazolin-3-one

B-3-6: 5-chloro-1,2-benzisothiazolin-3-one

With respect to these exemplified compounds, methods of synthesis andexample applications to other fields are described in U.S. Pat. Nos.2,767,172, 2,767,173, 2,767,174 and 2,870,015, British Patent No.848,130, French Patent No. 1,555,416 and other publications. Some ofthem are commercially available under trade names Topcide 300 andTopcide 600 (both produced by Permachem Asia), Finecide J-700 (producedby Tokyo Fine Chemical) and Proxel GXL (produced by I.C.I.).

The compounds represented by Formulae B-1 through B-3 are used in a of0.1 to 500 mg, preferably 0.5 to 100 mg per m² of light-sensitivematerial, and may be used in combination of two or more kinds.

The present invention is applicable to color photographiclight-sensitive materials such as color printing paper, color negativefilm, color reversal film, color reversal paper, direct positive colorprinting paper, color film for movie and color film for TV for ordinaryor movie use.

EXAMPLES

The present invention is hereinafter described in more detail by meansof the following examples, but the mode of embodiment of the inventionis not limited by these examples.

Example 1

The following layers with the compositions shown below were sequentiallyformed on a triacetyl cellulose film support in the order from thesupport side to yield a multiple layered color photographiclight-sensitive material sample No. 1.

The amount of addition in silver halide photographic light-sensitivematerial is expressed in gram per m², unless otherwise stated. Thefigures for silver halide and colloidal silver have been converted tothe amounts of silver. Figures for the amount of sensitizing dyes areshown in mol per mol of silver in the same layer.

    ______________________________________    Sample No. 1    ______________________________________    Layer 1: Anti-halation layer    Black colloidal silver 0.2    UV absorbent UV-1      0.23    High boiling solvent Oil-1                           0.18    Gelatin                1.4    Layer 2: First interlayer    Gelatin                1.3    Layer 3: Low speed red-sensitive emulsion layer    Silver iodobromide emulsion                           1.0    (average grain size 0.4 μm,    AgI content 2.0 mol %)    Sensitizing dye SD-1   1.8 × 10.sup.-5    Sensitizing dye SD-2   2.8 × 10.sup.-4    Sensitizing dye SD-3   3.0 × 10.sup.-4    Cyan coupler CCp-1     1.13 × 10-3 mol/m2    Colored cyan coupler CC-1                           0.066    DIR compound D-1       0.03    DIR compound D-3       0.01    High boiling solvent Oil-1                           0.64    Gelatin                1.2    Layer 4: Moderate speed red-sensitive emulsion layer    Silver iodobromide emulsion                           0.8    (average grain size 0.7 μm, AgI content 8.0    mol %, comprising AgBrI having an    average grain size r of 0.5 μm and an AgI    content of 7.0 mol %)    Sensitizing dye SD-1   2.1 × 10.sup.-5    Sensitizing dye SD-2   1.9 × 10.sup.-4    Sensitizing dye SD-3   1.9 × 10.sup.-4    Cyan coupler CCp-1     4.53 × 10-3 mol/m.sup.2    Colored cyan coupler CC-1                           0.027    DIR compound D-1       0.01    High boiling solvent Oil-1                           0.26    Gelatin                0.6    Layer 5: High speed red-sensitive emulsion layer    Silver iodobromide emulsion                           1.70    (average grain size 0.8 μm,    AgI content 8.0 mol %)    Sensitizing dye SD-1   1.9 × 10.sup.-5    Sensitizing dye SD-2   1.7 × 10.sup.-4    Sensitizing dye SD-3   1.7 × 10.sup.-4    Cyan coupler CCp-1     8.1 × 10.sup.-5 mol/m.sup.2    Cyan coupler CCp-2     3.04 × 10.sup.-4 mol/m.sup.2    Colored cyan coupler CC-1                           0.02    DIR compound D-1       0.025    High boiling solvent Oil-1                           0.21    Gelatin                1.2    Layer 6: Second interlayer    Gelatin                0.8    Layer 7: Low speed green-sensitive emulsion layer    Silver iodobromide emulsion                           1.1    (average grain size 0.4 μm,    AgI content 2.0 mol %)    Sensitizing dye SD-4   6.8 × 10.sup.-5    Sensitizing dye SD-5   6.2 × 10.sup.-4    Magenta coupler MCp-1  7.49 × 10.sup.-4 mol/m.sup.2    Magenta coupler MCp-2  2.83 × 10.sup.-4 mol/m.sup.2    Colored magenta coupler CM-1                           0.06    DIR compound D-2       0.017    DIR compound D-3       0.01    High boiling solvent Oil-2                           0.81    Gelatin                1.8    Layer 8: Moderate speed green-sensitive emulsion layer    Silver iodobromide emulsion                           0.7    (average grain size 0.7 μm,    AgI content 8.0 mol %)    Sensitizing dye SD-6   1.9 × 10.sup.-4    Sensitizing dye SD-7   1.2 × 10.sup.-4    Sensitizing dye SD-8   1.5 × 10.sup.-5    Magenta coupler MCp-1  9.7 × 10.sup.-5 mol/m.sup.2    Magenta coupler MCp-2  4.5 × 10.sup.-5 mol/m.sup.2    Colored magent coupler CM-1                           0.04    DIR compound D-2       0.018    High boiling solvent Oil-2                           0.30    Gelatin                0.8    Layer 9: High speed green-sensitive emulsion layer    Silver iodobromide emulsion                           1.7    (average grain size 1.0 μm,    AgI content 8.0 mol %)    Sensitizing dye SD-6   1.2 × 10.sup.-4    Sensitizing dye SD-7   1.0 × 10.sup.-4    Sensitizing dye SD-8   3.4 × 10.sup.-6    Magenta coupler MCp-1  1.25 × 10.sup.-4 mol/m.sup.2    Magenta coupler MCp-3  5.5 × 10.sup.-5 mol/m.sup.2    Colored magenta coupler CM-1                           0.04    High boiling solvent Oil-2                           0.31    Gelatin                1.2    Layer 10: Yellow filter layer    Yellow colloidal silver                           0.05    Antistaining agent SC-1                           0.1    High boiling solvent Oil-2                           0.13    Gelatin                0.7    Formalin scavenger HS-1                           0.09    Formalin scavenger HS-2                           0.07    Layer 11: Low speed blue-sensitive emulsion layer    Silver iodobromide emulsion having an                           0.5    average grain size of 0.4 μm and an AgI    content of 2.0 mol % and silver iodobromide    emulsion having an average grain size of    0.7 μm and an AgI content of 8.0 mol %    Sensitizing dye SD-9   5.2 × 10.sup.-4    Sensitizing dye SD-10  1.9 × 10.sup.-5    Yellow coupler YCp-1   1.55 × 10.sup.-3 mol/m.sup.2    Yellow coupler YCp-1   6.88 × 10.sup.-4 mol/m.sup.2    DIR compound D-1       0.03    High boiling solvent Oil-2                           0.24    Gelatin                1.3    Formalin scavenger HS-1                           0.08    Layer 12: High speed blue-sensitive emulsion layer    Silver iodobromide emulsion                           1.0    (average grain size 1.0 μm,    AgI content 8.0 mol %)    Sensitizing dye SD-9   1.8 × 10.sup.-4    Sensitizing dye SD-10  7.9 × 10.sup.-5    Yellow coupler YCp-1   3.59 × 10.sup.-4 mol/m.sup.2    Yellow coupler YCp-2   1.43 × 10.sup.-4 mol/m.sup.2    High boiling solvent Oil-2                           0.099    Gelatin                1.30    Formalin scavenger HS-1                           0.05    Formalin scavenger HS-2                           0.12    Layer 13: First protective layer    Fine grains of silver iodobromide emulsion                           0.4    (average grain size 0.08 μm,    AgI content 1 mol %)    UV absorbent UV-1      0.07    UV absorbent UV-2      0.10    High boiling solvent Oil-1                           0.07    High boiling solvent Oil-3                           0.07    Formalin scavenger HS-1                           0.13    Formalin scavenger HS-2                           0.37    Gelatin                1.3    Layer 14: Second protective layer    Alkali-soluble matting agent    (average grain size 2 μm)                           0.13    Polymethyl methacrylate    (average grain size 3 μm)                           0.02    Lubricant WAX-1        0.04    Gelatin                0.6    ______________________________________

In addition to these compositions, a coating aid Su-1, a dispersingagent Su-2, a viscosity controlling agent, hardeners H-1 and H-2, astabilizer ST-1, an antifogging agent AF-1 and two kinds of antifoggingagent AF-2 having average molecular weights of 10000 and 1100000,respectively, were added to appropriate layers.

The emulsions used to prepare the sample were all monodispersedemulsions having a lower value for surface silver iodide content, whichwere subjected to optimum sensitization with gold and sulfur inaccordance with a conventional method. Average grain size was calculatedby converting the projected image to a circle image within the samearea. ##STR31##

Next, film sample Nos. 2 through 8 were prepared using 2-equivalentcouplers for the present invention as shown in Table 1.

                                      TABLE 1    __________________________________________________________________________    Layer 3       Layer 4   Layer 5   Layer 7   Layer 8    Sample   Amount    Amount    Amount    Amount    Amount    No. Coupler             added*                  Coupler                       added*                            Coupler                                 added*                                      Coupler                                           added*                                                Coupler                                                     added*    __________________________________________________________________________    (2) C-24  5.66                  C-24 2.27 C-8  1.93 M-3  5.16 M-3  0.71    (3) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-3  5.16 M-3  0.71                            C-8  1.52    (4) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-18 5.16 M-18 0.71                            C-8  1.52    (5) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-23 5.16 M-23 0.71                            C-8  1.52    (6) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-18 5.16 M-18 0.71                            C-8  1.52    (7) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-18 5.16 M-18/                                                     0.65/                            C-8  1.52           MCp-3                                                     0.06    (8) CCp-1             11.32                  CCp-1                       4.53 CCp-1/                                 1.81/                                      M-18/                                           4.75/                                                M-18 0.71                            C-8  1.52 MCp-3                                           0.41    __________________________________________________________________________                       Layer 9   Layer 11  Layer 12                   Sample   Amount    Amount    Amount                   No. Coupler                            added*                                 Coupler                                      added*                                           Coupler                                                added*                                                     Remarks    __________________________________________________________________________                   (2) M-3  0.90 Y-2  11.2 Y-5  2.51 Inventive                   (3) M-3  0.90 Y-2/ 7.75/                                           Y-2/ 1.80/                                                     Inventive                                 Y-5  3.44 Y-5  0.71                   (4) M-3  0.90 Y-2/ 7.75/                                           Y-2/ 1.80/                                                     Inventive                                 Y-5  3.44 Y-5  0.71                   (5) M-18 0.90 Y-2/ 7.75 Y-2/ 1.80/                                                     Inventive                                 Y-5  3.44 Y-5  0.71                   (6) M-18/                            0.83/                                 Y-2/ 7.75/                                           Y-2/ 1.80/                                                     Inventive                       MCp-3                            0.07 Y-5  3.44 Y-5  0.71                   (7) M-18 0.90 Y-2/ 7.75/                                           Y-2/ 1.80/                                                     Inventive                                 Y-5  3.44 Y-5  0.71                   (8) M-18 0.90 Y-2/ 7.75 Y-2/ 1.80/                                                     Inventive                                 Y-5  3.44 Y-5  0.71    __________________________________________________________________________     *Expressed in 10.sup.-4 mol/m.sup.2

After the light-sensitive material samples thus prepared were subjectedto exposure through an optical wedge, a running processing was conductedunder the following conditions 1.

    ______________________________________              Processing      Processing                                       Amount of    Procedure time            temperature                                       replenisher    ______________________________________    Color     3     minutes   38° C.                                       775 ml    development              15    seconds    Bleaching 45    seconds   38° C.                                       155 ml    Fixation  1     minute    38° C.                                       400 ml              30    seconds    Stabilization              50    seconds   38° C.                                       270 ml    Drying    1     minute    40-70° C.                                       --    ______________________________________     Note:     Figures for the amount of replenisher are per m.sup.2 of lightsensitive     material.

Stabilization was conducted by the counter current method using fourbaths, in which the replenisher was supplied to the final stabilizingbath and the overflow therefrom was allowed to enter in the previousbath so that the entire overflow from the first stabilizing bath flew inthe fixing bath.

The processing solutions used in the above procedures had the followingcompositions:

    ______________________________________    Color developer    ______________________________________    Potassium carbonate         30.0   g    Sodium hydrogen carbonate   2.5    g    Potassium sulfite           3.0    g    Sodium bromide              1.2    g    Potassium iodide            0.6    mg    Hydroxylamine sulfate       2.5    g    Sodium chloride             0.6    g    4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)-                                4.6    g    aniline sulfate    Diethylenetriaminepentaacetic acid                                3.0    g    Potassium hydroxide         1.2    g    ______________________________________

Water was added to make a total quantity of 1 l, and potassium hydroxideor 20% sulfuric acid was added to obtain a pH of 10.01.

    ______________________________________    Color developer replenisher    ______________________________________    Potassium carbonate         40.0 g    Sodium hydrogen carbonate   3.0 g    Potassium sulfite           7.0 g    Sodium bromide              0.5 g    Hydroxylamine sulfate       3.1 g    4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)-                                6.0 g    aniline sulfate    Diethylenetriaminepentaacetic acid                                3.0 g    Potassium hydroxide         2.0 g    ______________________________________

Water was added to make a total quantity of 1 l, and potassium hydroxideor 20% sulfuric acid was added to obtain a pH of 10.12.

    ______________________________________    Bleacher    ______________________________________    Ferric ammonium 1,3-propylenediaminetetra-                               0.32   mol    acetate    Disodium ethylenediaminetetraacetate                               10     g    Ammonium bromide           100    g    Glacial acetic acid        40     g    Ammonium nitrate           40     g    ______________________________________

Water was added to make a total quantity of 1 l, and aqueous ammonia orglacial acetic acid was added to obtain a pH of 4.4.

    ______________________________________    Bleacher replenisher    ______________________________________    Ferric ammonium 1,3-propylenediaminetetra-                               0.35   mol    acetate    Disodium ethylenediaminetetraacetate                               2      g    Ammonium bromide           120    g    Ammonium nitrate           50     g    Glacial acetic acid        40     g    ______________________________________

Water was added to make a total quantity of 1 l, and aqueous ammonia orglacial acetic acid was added to obtain a pH of 3.4.

    ______________________________________    Fixer and fixer replenisher    ______________________________________    Ammonium thiocyanate       120 g    Ammonium thiosulfate       200 g    Anhydrous sodium bisulfite 20 g    Sodium metabisulfite       4.0 g    Disodium ethylenediaminetetraacetate                               1.0 g    ______________________________________

Water was added to make a total quantity of 1 l, and glacial acetic acidand aqueous ammonia were added to obtain a pH of 6.5.

    ______________________________________    Stabilizer and stabilizer replenisher    ______________________________________    Surfactant (listed in Table 2)                            See Table 2    *Dearcide* 702 (*Dearborn*)                            1.0 ml    Formaldehyde            See Table 2    ______________________________________

Water was added to make a total quantity of 1 l, and potassium hydroxideor 20% sulfuric acid were added to obtain a pH of 8.5. Runningprocessing was carried out using a compact developing machine until theamount of the stabilizer replenisher supplied reached two times thestabilizing bath tank capacity.

After completion of running processing, each stabilizing bath wasexamined for the occurrence of sulfides and occurrence of deposits onthe inside wall thereof. Also, the magenta density in minimum densityportion (Dmin(G)) and reticulation were examined in the film sampleafter processing. The results are shown in Table 2.

The evaluation criteria used are as follows.

1) Occurrence of sulfides in fixer

A: No occurrence.

B: Suspended matter noted on and in the fixer, but no problem.

C: Sulfides noted on and in the fixer, may pose a practical problem.

D: Precipitation and solid deposition in rack liquid interface.

The more the number of D marks, the more precipitation and soliddeposition.

2) Reticulation

A: No occurrence.

B: Reticulation noted in several sites per roll of 24-shot film, butabsolutely no problem.

C: More frequent reticulation than B, but no problem.

D: Still more frequent reticulation, posing a problem.

The more the number of D marks, the more frequently reticulation occurs.

                                      TABLE 2    __________________________________________________________________________    Experi-        Film             Stabilizer    ment        sample            Stabilizer surfactant                         formaldehyde         Sulfides    No. No. (amount added)                         (amount added)                                 ΔD.sub.min (G)*                                       Reticulation                                              in fixer                                                   Remarks    __________________________________________________________________________    1-1 (1) (II-3) (0.3 g/l)                         0.00    0.00  C      B    Comparative                                 (reference                                 value)    1-2 (2) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-3 (3) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-4 (4) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-5 (5) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-6 (6) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-7 (7) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-8 (8) (II-3) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-9 (2) Not added    0.00    +0.02 C-D    C    Comparative    1-10        (2) Ethylene glycol (3.0 g/l)                         0.00    +0.01 C      B-C  Comparative    1-11        (2) Diethylene glycol (3.0 g/l)                         0.00    ±0.00                                       C      B-C  Comparative    1-12        (2) TEAC (1.0 g/l)                         0.00    +0.01 C      B-C  Comparative    1-13        (2) DTMAC (1.0 g/l)                         0.00    ±0.00                                       C      B-C  Comparative    1-14        (2) LMTS (1.0 g/l)                         0.00    +0.01 C      B-C  Comparative    1-15        (2) DBSS (1.0 g/l)                         0.00    -0.01 C      B-C  Comparative    1-16        (2) (I-1) (3.0 g/l)                         0.00    -0.02 B      B    Inventive    1-17        (2) (I-5) (3.0 g/l)                         0.00    -0.02 B      B    Inventive    1-18        (2) (I-6) (3.0 g/l)                         0.00    -0.01 B      B    Inventive    1-19        (2) (I-12) (3.0 g/l)                         0.00    -0.02 B      B    Inventive    1-20        (2) (II-14) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-21        (2) (II-4) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-22        (2) (II-8) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-23        (2) (II-12) (0.3 g/l)                         0.00    -0.01 B      B    Inventive    1-24        (2) (II-15) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-25        (2) (II-16) (0.3 g/l)                         0.00    -0.02 B      B    Inventive    1-26        (2) (II-3) (0.3 g/l)                         0.60    -0.02 A      DD   Comparative    1-27        (2) (II-3) (0.3 g/l)                         0.30    -0.02 B      D    Comparative    1-28        (2) (II-3) (0.3 g/l)                         0.20    -0.02 B      B    Inventive    1-29        (2) (II-3) (0.3 g/l)                         0.10    -0.02 B      B    Inventive    __________________________________________________________________________     Note:     TEAC denotes triethylammonium chloride;     DTMAC denotes dodecyltrimethylammonium chloride;      LMTS denotes sodium lauroylmethyltaurate;     DBSS denotes sodium dodecylbenzenesulfonate.     *ΔD.sub.min (G) = D.sub.min (G) - D.sub.min (G) reference     D.sub.min (G) reference is the minimum magenta density of sample No. 11.

It is evident from Table 2 that when the entire overflow from stabilizerwas allowed to enter in the fixing bath, the samples according to thepresent invention were generally better than the comparative sampleswith respect to magenta density at minimum density portion, reticulationand occurrence of sulfides in the fixing bath.

Treated samples from Experiment Nos. 1-1 through 1-8 were stored at atemperature of 80° C. and a relative humidity of 75% for 10 days andtested for maximum magenta density and dye fading rate. Thelight-sensitive material samples according to the present inventionproved better than the comparative sample No. 1 even when the stabilizercontained substantially no formaldehyde. Also found was that the filmsprocessed with a surfactant according to the invention has no back facestain or uneven wetting.

Example 2

The light-sensitive material sample used in Example 1 was subjected tocontinuous processing under the following conditions 2.

    ______________________________________              Processing      Processing                                       Amount of    Procedure time            temperature                                       replenisher    ______________________________________    Color     3     minutes   38 ± 0.3° C.                                       536 ml    development              15    seconds    Bleach-   4     minutes   38 ± 2.0° C.                                       730 ml    fixation  15    seconds    Stabilization              1     minute    38 ± 5.0° C.                                       270 ml    Drying    1     minute    55 ± 5.0° C.                                       --    ______________________________________     Note:     Figures for the amount of replenisher are per m.sup.2 of lightsensitive     material.

The color developer, bleach-fixer, stabilizer and replenishers used areshown below. Stabilization was conducted by the counter current methodusing four baths, in which the replenisher was supplied to the finalbath.

    ______________________________________    Color developer and replenisher    The same as used in Example 1.    Bleach-fixer    Water                      800    ml    Ferric ammonium ethylenediaminetetraacetate                               80     g    Ferric ammonium diethylenetriaminepenta-                               100    g    acetate    Ethylenediaminetetraacetic acid                               2      g    Ammonium sulfite           20     g    Ammonium thiosulfate       150    g    Ammonium thiocyanate       120    g    Aqueous ammonia (25%)      12     ml    ______________________________________

After adjusting to a pH of 6.5 with aqueous ammonia or acetic acid,water was added to make a total quantity of 1 l.

    ______________________________________    Bleach-fixer replenisher    ______________________________________    Water                      700    ml    Ferric ammonium ethylenediaminetetraacetate                               130    g    Ferric ammonium diethylenetriaminepenta-                               150    g    acetate    Ethylenediaminetetraacetic acid                               2      g    Ammonium sulfite           30     g    Ammonium thiosulfate       180    g    Ammonium thiocyanate       150    g    Aqueous ammonia (25%)      15     ml    ______________________________________

After adjusting to a pH of 6.0 with aqueous ammonia or acetic acid,water was added to make a total quantity of 1 l.

Stabilizer and stabilizer replenisher

The same as used in Example 1.

Before proceeding to continuous processing, the bleaching bath andfixing bath of the automatic developing machine used in Example 1 werecombined to a single bath for bleach-fixation. The other conditions ofcontinuous processing and experimental conditions were the same as inExample 1, followed by evaluation in the same manner as in Example 1.The results obtained were similar to those obtained in Example 1.

Example 3

After the film sample No. 2 prepared in Example 1 was subjected toimagewise exposure, a running processing was conducted under thefollowing conditions 3 in various amounts of stabilizer replenisheradded.

    ______________________________________               Processing Processing Amount of    Procedure  time       temperature                                     replenisher    ______________________________________    Color       3 minutes 38° C.                                     775 ml    development               15 seconds    Bleaching  45 seconds 38° C.                                     155 ml    Fixation    1 minute  38° C.                                     400 ml               30 seconds    Stabilization               50 seconds 38° C.                                     See Table 3    Drying      1 minute  40-70° C.                                     --    ______________________________________     Note: Figures for the amount of replenisher are per m.sup.2 of     lightsensitive material.

Stabilization was conducted by the counter current method using fourbaths, in which the replenisher was supplied to the final stabilizingbath and the overflow therefrom was allowed to enter in the precedingbath so that the entire overflow from the first stabilizing bath flew inthe fixing bath.

The processing solutions and replenishers used were the same as inExample 1.

                                      TABLE 3    __________________________________________________________________________                    Amount of    Experi-        Film            Stabilizer                    stabilizer    ment        sample            surfactant                    formaldehyde                            replenisher        Sulfides    No. No. (amount added)                    (amount added)                            (ml/m.sup.2)                                  ΔD.sub.min (G)*                                        Reticulation                                               in fixer                                                    Remarks    __________________________________________________________________________    3-1 (2) (II-3) (0.3 g/l)                    0.00    700   ±0.00                                        B      B    Inventive    3-2 (2) (II-3) (0.3 g/l)                    0.00    670   ±0.00                                        B      B    Inventive    3-3 (2) (II-3) (0.3 g/l)                    0.00    500   ±0.00                                        B      B    Inventive    3-4 (2) (II-3) (0.3 g/l)                    0.00    270   +0.01 B      B    Inventive    3-5 (2) Not added                    0.00    700    0.00 B      B    Comparative                                  (reference                                  value)    3-6 (2) Not added                    0.00    670   +0.02 C      B-C  Comparative    3-7 (2) Not added                    0.00    500   +0.03 C      C    Comparative    3-8 (2) Not added                    0.00    270   +0.05 C-D    C    Comparative    __________________________________________________________________________     *ΔD.sub.min (G) = D.sub.min (G) - D.sub.min (G) reference     D.sub.min (G) reference is the value for sample No. 35.

Evaluation was made in the same manner as in Example 1. The results aregiven in Table 3.

It is evident from Table 3 that the effect of the invention ofsuppressing increase in minimum magenta density is enhanced when theamount of replenisher is not more than 670 ml/m².

Example 4

The film samples listed in Table 4 were prepared in the same manner aswith the film sample No. 2 prepared in Example 1 except that the totalamount of silver coated was varied.

                  TABLE 4    ______________________________________                    Total amount of    Film sample No. silver coated    ______________________________________     9              1.0    10              2.0    11              3.0    12              4.0    13              8.0    14              10.0    15              11.0    ______________________________________

The film samples thus prepared were processed in the same manner as inExperiment No. 1-2 in Example 1 and evaluated in the same manner as inExample 1. Also, maximum cyan dye density and fixability weredetermined. The results are summarized in Table 5.

                  TABLE 5    ______________________________________                            Stability       Occur-    Experi-          Film              (residual       rence of    ment  sample            silver)  Reticula-                                            sulfides    No.   No.     ΔD.sub.max (R)                            (mg/100 cm.sup.2)                                     tion   in fixer    ______________________________________    5-1    2      0.00      0.1      B      B                  (reference                  value)    5-2    9      -0.49     0.1      B      B    5-3   10      -0.29     0.0      B      B    5-4   11      -0.11     0.0      B      B    5-5   12      -0.03     0.0      B      B    5-6   13      ±0.00  0.1      B      B    5-7   14      ±0.00  2.0      C-B    C-B    5-8   15      ±0.00  4.0      C      C    ______________________________________     *ΔD.sub.max (R) = D.sub.max (R) - D.sub.max (R) reference

As is evident from Table 5, for enhancing the effect of the inventionwithout being accompanied by degradation of photographic performance,the amount of silver contained in film sample is preferably not lessthan 2 g/m² and not more than 10 g/m², more preferably 4 to 8 g/m².

Example 5

To the film sample No. 2 prepared in Example 1 was added a compoundlisted in Table 6 to 10 mg/m² and tested in the same manner as inExperiment No. 1-2 in Example 1. The results are summarized in Table 6.

                  TABLE 6    ______________________________________    Experi-                              Occurrence    ment                          Reticula-                                         of sulfides    No.   Compound added                        ΔD.sub.min (G)                                  tion   in fixer    ______________________________________    6-1   Not added     -0.02     B      B    6-2   Phenol        -0.02     B      B    6-3   Dehydroacetic -0.03     C-B    B          acid    6-4   Thiazolyl-    -0.02     B      B          benzimidazole    6-5   Chlorodiphenyl                        -0.01     B      B    6-6   Cresol        -0.03     B      B    6-7   p-amino-benzene-                        -0.02     B      B          sulfamide    6-8   B-1-1         +0.00     A      B-A    6-9   B-1-16        +0.00     A      B-A    6-10  B-1-18        +0.01     A      B-A    6-11  B-2-1         +0.02     A      B-A    6-12  B-2-2         +0.00     A      B-A    6-13  B-2-7         +0.00     A      B-A    6-14  B-2-10        +0.01     A      B-A    6-15  B-3-1         +0.01     A      B-A    6-16  B-3-6         +0.00     A      B-A    ______________________________________

As seen in Table 6, the effect of the invention is enhanced when acompound represented by one of Formulas B-1 through B-3 is used incombination with the light-sensitive material for the processing methodof the invention.

The present invention provides a processing method for silver halidecolor photographic light-sensitive material which offers good dye imagepreservability and improved staining in the unexposed portion and whichpermits waste liquid reduction and is hence excellent from thesocioenvironmental viewpoint.

What is claimed is:
 1. A processing method for a silver halide colorphotographic light-sensitive material comprising(a) processing saidmaterial with a fixing solution, (b) processing said material with astabilizing solution having a pH of 7.5 to 10, and then about 270 ml toabout 800 ml of the overflow from the said stabilizing solution areallowed to enter into said fixing solution and said stabilizer containssubstantially no formaldehyde but contains a compound represented byFormula I or Formula II, wherein said silver halide color photographiclight-sensitive material comprising:(I) a coupler represented by Formula2eq-1, (II) the total amount of silver coated in said silver halidecolor photographic light sensitive material is not less than 2 g per m²of said light-sensitive material; and (III) a compound represented byFormula B-3; ##STR32## wherein Cp represents a coupler residue; *represents a coupler coupling site; X represents a group which splitsoff upon dye formation by coupling with the oxidation product of anaromatic primary amine based color developing agent; ##STR33## whereinR₁ represents a monovalent organic group, R₂ represents an ethylenegroup, a trimethylene group or a propylene group, m represents aninteger of 4 to 50, X₁ represents a hydrogen atom, --SO₃ M or --PO₃ M₂,wherein M represents a hydrogen atom, an alkali metal or an ammoniumgroup: ##STR34## wherein R₉ represents a hydrogen atom, a hydroxylgroup, a lower alkyl group, an alkoxyl group, or ##STR35## R₁₀, R₁₁, andR₁₂ independently represent a hydrogen atom or a lower alkyl group,whether identical or not; 11 through 13 independently represent aninteger of 0 to 30; p, q¹ and q² independently represent an integer of 0to 30; X₁ and X₂ independently represent --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --,##STR36## wherein R₇ represents a hydrogen atom, a halogen atom, analkyl group, an aryl group, a halogenated alkyl group, an arylalkylgroup, --R¹⁵ --OR¹⁶, --CONHR¹⁷, (where R¹⁵ represents an alkylene group,R₁₆ and R₁₇ each represent a hydrogen atom, or an alkyl group; and R₈,R₉, R₁₀ and R₁₁ each represent a hydrogen atom, a halogen atom, ahydroxyl group, an alkyl group, an amino group, or a nitro group.
 2. Theprocessing method for silver halide color photographic light-sensitivematerial of claim 1 wherein the total amount of silver coated in saidsilver halide color photographic light-sensitive material is not lessthan 2 g per m² of light-sensitive material.
 3. The processing methodfor silver halide color photographic light-sensitive material of claim 2wherein said silver halide color photographic light-sensitive materialcontains a compound represented by the following formulae B-1 throughB-3, ##STR37## wherein R₁ represents an alkyl group, a cycloalkyl group,an aryl group, a hydroxy group, an alkoxycarbonyl group, an amino group,a carboxylic acid group (including its salt) or a sulfonic acid group(including its salt); R² and R³ independently represent a hydrogen atom,a halogen atom, an amino group, a nitro group, a hydroxy group, analkoxycarbonyl group, a carboxylic acid group (including its salt) or asulfonic acid group (including its salt), M represents a hydrogen atom,an alkali metal or an ammonium group; ##STR38## wherein R⁴ represents ahalogen atom, an alkyl group, an aryl group, a halogenated an alkylgroup, --R¹², --OR¹³, CONHR¹⁴ (R¹² represents a hydrogen atom, an alkylgroup or an arylalkyl group) or an arylalkyl group; R⁵ and R⁶independently represent a hydrogen atom, a halogen atom, halogenatedalkyl group or alkyl group; R⁸, R⁹, R¹⁰, and R¹¹ independently representhydrogen, halogen, hydroxyl, alkyl, amino or nitro.